Cleaning implement

ABSTRACT

A cleaning implement includes an erodible foam adapted to contact a surface to be cleaned and a hydrophobic film attached to the erodible foam. The erodible foam is adhered to the hydrophobic film with an adhesive attachment. The cleaning implement may also include a handle attached to the impermeable film.

FIELD OF THE INVENTION

The invention relates to a cleaning implement comprising erodible foam that is adapted to contact a surface to be cleaned and a hydrophobic film adhered to the erodible foam with an adhesive attachment. The cleaning implement may also include a handle attached to the hydrophobic film.

BACKGROUND OF THE INVENTION

Use of an erodible foam, such as melamine-formaldehyde resin foam (“melamine foam”) for hard surface cleaning is well known. Cleaning implements of cut or molded melamine foam are popular for removing soils and stains from hard surfaces. Melamine foams are currently marketed in some countries under the tradename of Mr. Clean Magic Eraser™. Melamine foams, when wetted with an appropriate solvent, show excellent soil and stain removal in cleaning hard surfaces. Although melamine foam is generally effective in removing soils and stains from hard surfaces, consumers may find it difficult to remove certain kinds of tough stains with melamine foam, even after applying extra rubbing force.

To improve the cleaning performance of melamine foam over tough stains, one may use a detergent composition along with the melamine foam to clean. The sponge and detergent can be provided separately or the sponge may be impregnated with the detergent. Consumers may still find it inconvenient to apply the detergent and then scrub. Further, sponges impregnated with detergents tend to release the active agents quickly, leading to significant loss of the active agent after the first several uses. In turn, reduced cleaning properties are observed as the active agent is used up. Also, when an active agent releases quickly in the first or second use, the high level of active agent may require extra rinsing.

Further, to help improve the cleaning performance of melamine foam over tough stains, one may also use a handle along with the melamine foam to clean. However, known melamine foams provided with a handle utilize hydrophilic and/or porous materials to attach the handle to the melamine foam. Unfortunately, these cleaning implements suffer from a number of drawbacks. Namely, utilizing hydrophilic and/or porous materials to attach a handle to the melamine foam enables liquid and/or materials to flow to the underside of the handle and therefore enables the build-up of bacteria, mold and other undesirable thereto. Thus, there remains a need for a cleaning implement which is able to clean tough stains while minimizing liquid and/or materials to flow there through and, when used with a handle, to the underside of the handle.

SUMMARY OF THE INVENTION

The present invention, in one embodiment, relates to a cleaning implement comprising an erodible foam adapted to contact a surface to be cleaned, and a hydrophobic film attached to the erodible foam. The erodible foam is adhered to the hydrophobic film with an adhesive attachment. In this embodiment, the cleaning implement may also include a handle attached to the hydrophobic film.

In another embodiment, the present invention relates to a cleaning implement comprising an erodible foam adapted to contact a surface to be cleaned, and an impermeable film attached to the erodible foam. The erodible foam is adhered to the film with an adhesive attachment. In this embodiment, the cleaning implement may also include a handle attached to the impermeable film.

The present invention further encompasses a method of cleaning a surface with the aforementioned cleaning implement.

It has now been surprisingly found that by providing a cleaning implement comprising an erodible foam adapted to contact a surface to be cleaned, and an impermeable film adhered to the film with an adhesive attachment enables cleaning of tough stains while minimizing liquid and/or materials to flow there through and, when used with a handle, to the underside of the handle. As a result, when used with a handle, the present cleaning implement prevents bacteria, mold and other undesirables to flow to the underside of the handle.

BRIEF DESCRIPTION OF THE DRAWINGS

The detailed description of the drawings particularly refers to the accompanying figures in which:

FIG. 1 is a perspective view of an embodiment of the cleaning implement herein with an erodible foam substrate, a hydrophobic and/or impermeable film attached to the erodible foam and a handle; and

FIG. 2 is a perspective view of the hydrophobic and/or impermeable film attached to the erodible foam substrate as show in the cleaning implement of FIG. 1.

DETAILED DESCRIPTION OF THE INVENTION

The cleaning implement 10 according to the present invention include an erodible foam 20 adapted to contact a surface to be cleaned and a hydrophobic and/or impermeable film 30 attached to the erodible foam 20. The erodible foam 20 is adhered to the hydrophobic and/or impermeable film with an adhesive attachment 40. The cleaning implement 10 may also include a handle 50 attached to the hydrophobic and/or impermeable film 30.

Erodible Foam

The erodible foam 20 herein is an article of manufacture of any suitable shape, size, and/or volume suitable for removing spots and/or stains from surfaces. The erodible foam substrate 20, in one embodiment, is a heat-compressed erodible foam substrate 20. By “heat-compressed”, it is meant that the erodible foam 20 has been subject to two distinct operations: a heating step and a compression step. “Erodible foam” herein means foam which crumbles into small particles and peels off by friction. Suitable erodible foam includes, but is not limited to, melamine foam, phenolic foam, etc. According to one embodiment of the present invention, the erodible foam 20 is a heat-compressed melamine.

Principles for manufacturing melamine-based foams and compressed melamine-based foams are well known. Melamine-based foams are currently manufactured by BASF (Ludwigshafen, Germany) under the BASOTECT® brand name. For example, BASOTECT® 2011, with a density of about 0.01 g/cm3, may be used. Blocks of melamine-based foam for cleaning are marketed by Procter & Gamble (Cincinnati, Ohio) under the MR. CLEAN® brand name, and under the CLEENPRO™ name by LEC, Inc. of Tokyo, Japan (several product executions are shown at http://www.users.bigpond.com/jmc.au/CLEENPRO/CLEENPRO-E.htm and http://www.users.bigpond.com/jmc.au/CLEENPRO/CLEENPRO%20Family-E.htm, both printed on Nov. 13, 2003). Melamine-based foam is also marketed for acoustic and thermal insulation by many companies such as American Micro Industries (Chambersburg, Pa.).

Principles for production of melamine-based foam are also disclosed by H. Mahnke et al. in EP-B 071 671, published Dec. 17, 1979. According to EP-B 017 671, they are produced by foaming an aqueous solution or dispersion of a melamine-formaldehyde condensation product which comprises an emulsifier (e.g., metal alkyl sulfonates and metal alkylaryl sulfonates such as sodium dodecylbenzene sulfonate), an acidic curing agent, and a blowing agent, such as a C5-C7 hydrocarbon, and curing the melamine-formaldehyde condensate at an elevated temperature. The foams are reported to have the following range of properties:

a density according to DIN 53 420 between 4 and 80 grams per liter (g/l), corresponding to a range of 0.004 g/cc to 0.08 g/cc (though for purposes of the present invention the density can also range from about 0.006 g/cc to about 0.1 g/cc, or other useful ranges);

a thermal conductivity according to DIN 52 612 smaller than 0.06 W/m ° K;

a compression hardness according to DIN 53 577 under 60% penetration, divided by the density, yielding a quotient less than 0.3 (N/cm2)/(g/l), and preferably less than 0.2 (N/cm2)/(g/l), whereby after measurement of compression hardness the thickness of the foam recovers to at least 70% and preferably at least 90% of its original thickness;

an elasticity modulus according to DIN 53 423, divided by the density of the foam, under 0.25 (N/mm2)/(g/l) and preferably under 0.15 (N/mm2)/(g/l);

a bending path at rupture according to DIN 53 423 greater than 6 mm and preferably greater than 12 mm; and

a tensile strength according to DIN 53 571 of at least 0.07 N/mm2 or preferably at least 0.1 N/mm2.

The foam may be molded or shaped into three-dimensional shapes for aesthetic or functional purposes. For example, melamine-based foam may be thermally molded according to the process disclosed in U.S. Pat. No. 6,608,118, “Melamine Molded Foam, Process for Producing the Same, and Wiper,” issued Aug. 19, 2003 to Y. Kosaka et al., herein incorporated by reference, which discloses molding the foam at 210 to 350 C (or, more particularly, from 230° C. to 280° C. or from 240° C. to 270° C.) for 3 minutes or longer to cause plastic deformation under load, wherein the foam is compressed to a thickness of about 1/1.2 to about 1/12 the original thickness, or from about 1/1.5 to about 1/7 of the original thickness.

As described by Kosaka et al., the melamine-based foam can be produced by blending major starting materials of melamine and formaldehyde, or a precursor thereof, with a blowing agent, a catalyst and an emulsifier, injecting the resultant mixture into a mold, and applying or generating heat (e.g., by irradiation or electromagnetic energy) to cause foaming and curing. The molar ratio of melamine to formaldehyde (i.e., melamine:formaldehyde) for producing the precursor is said to be 1:1.5 to 1:4, or more particularly 1:2 to 1:3.5. The number average molecular weight of the precursor can be from about 200 to about 1,000, or from about 200 to about 400. Formalin, an aqueous solution of formaldehyde, can be used as a formaldehyde source.

As monomers for producing the precursor, according to Kosaka et al., the following monomers may be used in an amount of 50 parts by weight (hereinafter abbreviated as “parts”) or less, particularly 20 parts by weight or less, per 100 parts by weight of the sum of melamine and formaldehyde. Melamine is also known by the chemical name 2,4,6-triamino-1,3,5-triazine. As other monomers corresponding to melamine, there may be used C1-5 alkyl-substituted melamines such as methylolmelamine, methylmethylolmelamine and methylbutylolmelamine, urea, urethane, carbonic acid amides, dicyandiamide, guanidine, sulfurylamides, sulfonic acid amides, aliphatic amines, phenols and the derivatives thereof. As aldehydes, there may be used acetaldehyde, trimethylol acetaldehyde, acrolein, benzaldehyde, furfurol, glyoxal, phthalaldehyde, terephthalaldehyde, and the like.

As the blowing agent, there may be used pentane, trichlorofluoromethane, trichlorotrifluoroethane, etc. As the catalyst, by way of example, formic acid may be used and, as the emulsifier, anionic surfactants such as sodium sulfonate may be used.

The amount of the electromagnetic energy to be irradiated for accelerating the curing reaction of the reaction mixtures can be adjusted to be from about 500 to about 1,000 kW, or from about 600 to 800 kW, in electric power consumption based on 1 kg of an aqueous formaldehyde solution charged in the mold. If the electric power applied is insufficient, there may be insufficient foaming, leading to production of a cured product with a high density. On the other hand, in case when the electric power consumption is excessive, the pressure upon foaming becomes high, leading to significant exhaust flows from the mold and even the possibility of explosion.

Other useful methods for producing melamine-based foam are disclosed in U.S. Pat. No. 5,413,853, “Melamine Resin Foam,” issued May 9, 1995 to Y. Imashiro et al., herein incorporated by reference. According to Imashiro et al., a melamine resin foam can be obtained by coating a hydrophobic component on a known melamine-formaldehyde resin foam body obtained by foaming a resin composition composed mainly of a melamine-formaldehyde condensate and a blowing agent. The components used in the present melamine resin foam can therefore be the same as those conventionally used in production of melamine-formaldehyde resins or their foams, except for the hydrophobic component.

As an example, Imashiro et al. disclose a melamine-formaldehyde condensate obtained by mixing melamine, formalin and paraformaldehyde and reacting them in the presence of an alkali catalyst with heating. The mixing ratio of melamine and formaldehyde can be, for example, 1:3 in terms of molar ratio.

The melamine-formaldehyde condensate can have a viscosity of about 1,000-100,000 cP, more specifically 5,000-15,000 cP and can have a pH of 8-9.

As the blowing agent, a straight-chain alkyl hydrocarbon such as pentane or hexane is disclosed.

In order to obtain a homogeneous foam, the resin composition composed mainly of a melamine-formaldehyde condensate and a blowing agent may contain an emulsifier. Such an emulsifier includes, for example, metal alkylsulfonates and metal alkylarylsulfonates.

The resin composition may further contain a curing agent in order to cure the foamed resin composition. Such a curing agent includes, for example, acidic curing agents such as formic acid, hydrochloric acid, sulfuric acid and oxalic acid.

The foam disclosed by Imashiro et al. can be obtained by adding as necessary an emulsifier, a curing agent and further a filler, etc. to the resin composition composed mainly of a melamine-formaldehyde condensate and a blowing agent, heat-treating the resulting mixture at a temperature equal to or higher than the boiling point of the blowing agent to give rise to foaming, and curing the resulting foam.

In another embodiment, the foam material may comprise a melamine-based foam having an isocyanate component (isocyanate-based polymers are generally understood to include polyurethanes, polyureas, polyisocyanurates and mixtures thereof). Such foams can be made according to U.S. Pat. No. 5,436,278, “Melamine Resin Foam, Process for Production Thereof and Melamine/Formaldehyde Condensate,” issued Jul. 25, 1995 to Imashiro et al., herein incorporated by reference, which discloses a process for producing a melamine resin foam comprising a melamine/formaldehyde condensate, a blowing agent and an isocyanate. One embodiment includes the production of a melamine resin foam obtained by reacting melamine and formaldehyde in the presence of a silane coupling agent. The isocyanate used in U.S. Pat. No. 5,436,278 can be exemplified by CR 200 (a trademark of polymeric-4,4′-diphenylmethanediisocyanate, produced by Mitsui Toatsu Chemicals, Inc.) and Sumidur E211, E212 and L (trademarks of MDI type prepolymers, produced by Sumitomo Bayer Urethane Co., Ltd). One example therein comprises 100 parts by weight of melamine/formaldehyde condensate (76% concentration), 6.3 parts sodium dodecylbenzenesulfonate (30% concentration), 7.6 parts pentane, 9.5 parts ammonium chloride, 2.7 parts formic acid, and 7.6 parts CR 200. A mixture of these components is placed in a mold and foamed at 1 00° C., yielding a material with a density of 26.8 kg/m3 (0.0268 g/cm3), a compression stress of 0.23 kgf/cm2, and a compression strain of 2.7%. In general, the melamine-based foams of U.S. Pat. No. 5,436,278 typically have a density of 25-100 kg/m3, a compression strain by JIS K 7220 of 2.7%-4.2% (this is said to be improved by about 40%-130% over the 1.9% value of conventional fragile melamine foams), and a thermal conductivity measured between 10° C. to 55° C. of 0.005 kcal/m-h-° C. or less (this is far smaller than 0.01 kcal/m-h-° C. which is said to be the value of conventional fragile foam). Other foams comprising melamine and isocyanates are disclosed in WO 99/23160, “Composition and Method for Insulating Foam,” published May 14, 1999 by Sufi, the U.S. equivalent (application U.S. Pat. No. 9,823,864) is herein incorporated by reference.

Suitable shapes of the erodible foam 20 herein may be selected from the group consisting of a cubic shape, a rectangular shape, a pyramidal shape, a cylindrical shape, a conical shape, an oblique rectangular prism shape, a cuboid shape, a tetrahedron shape, a sphere shape, a globular shape, and an ellipsoid shape. “Oblique rectangular prism shape” herein means a voluminous body having six walls, wherein three pairs of parallel and equally shaped and sized walls exist and wherein one pair of walls are in the shape of a parallelogram and the remaining two pairs of walls are of rectangular shape.

Film

The film 30 may comprise any sheet which is flexible, impermeable to fluid and, in one embodiment, hydrophobic. As used herein, the term “impermeable” means that the material resists and, in some embodiments, prevents diffusion of moisture therethrough. The erodible foam 20 is adhered to the hydrophobic and/or impermeable film 30 with an adhesive attachment 40, as discussed in further detail herein, and mirrors the overall shape, as discussed above, of the erodible foam 20. In one embodiment, the film 30 removably joins the erodible foam 20 to a handle 50 and, in another embodiment, the film 30 may be permanently joined to the erodible foam 20. In another embodiment, the film 30 is printable or, in other words, is capable of being printed on.

The film 30 may comprise one or more layers. The layer may comprise a film, a synthetic nonwoven, a cellulosic sheet, sustainable sheets and combinations thereof. Plural layers may comprise one or more of these materials and laminates thereof, including the same and/or different materials.

If a film 30 is elected for one or more of the layers, the film may comprise a polyolefinic sheet, as is known in the art. The sheet may comprise polyethylene terephthalate, polypropylene, polyethylene naphthalate, low-density polyethylene, high-density polyethylene, etc. as are known in the art. The film layer may be smooth or textured, as described in commonly assigned U.S. Pat. No. 4,846,821. A film layer may have a basis weight of about 15 to about 60 gsm and/or a thickness ranging from about 0.01 to about 3 mm.

A synthetic nonwoven may be carded, thermally bonded, spunbonded, hydroentagled, etc., as are known in the art. The nonwoven may be of constant or variable basis weight and/or density. The nonwoven may be textured and/or comprise discrete apertures, as disclosed in commonly assigned U.S. Pat. No. 6,936,330. A nonwoven layer may have a basis weight of about 15 to about 120 gsm and/or a thickness ranging from about 0.01 to 3 mm.

A cellulosic sheet may be wet laid and comprise permanent and/or temporary wet strength resins, as are known in the art. The cellulosic sheet may comprise kraft grade or tissue grade paper. The cellulosic sheet may be of constant or variable basis weight and/or density, as disclosed in commonly assigned U.S. Pat. No. 5,277,761 or commonly assigned U.S. Pat. No. 4,637,859. A tissue grade cellulosic sheet may have a basis weight of about 15 to about 45 gsm and/or a thickness ranging from about 0.01 to about 3 mm.

If desired, the one or more of the layers may be made of sustainable materials and/or combinations and blends of sustainable and other materials, including polymers derived from Biorenewable materials. Sustainable materials may include polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), an aliphatic-aromatic copolyester optionally with high terephthalic acid content, an aromatic copolyester optionally with high terephthalic acid content, polyhydroxyalkanoate (PHA), thermoplastic starch (TPS) and mixtures thereof. Suitable materials are disclosed in commonly assigned U.S. Pat. No. 8,083,064.

If desired, the film 30 may comprise a laminate of two or more materials. For example, the film 30 may comprise a layer of polyolefinic film. This layer may be reinforced with a woven layer or yarn layer attached thereto. A woven layer may comprise a loose weave, providing loop material suitable for attachment to a hook surface. A yarn layer may comprise plural parallel or randomly laid yards, also providing loop material suitable for attachment to a hook surface. The woven and/or yarn layers may be thermally bonded to the film 30 layer.

Adhesive

The adhesive attachment 40 may be either permanent (wherein the erodible foam 20 and film 30 cannot be separated without inflicting substantial damage to either the foam or film) or temporary (wherein the erodible foam 20 and film 30 may be separated without inflicting substantial damage to either the foam or film) as desired. Suitable permanent attachments include permanent adhesive, foam flame lamination, sewing or needle-punching the substrates and/or films together, and a combination thereof. The substrates or films can also be joined together by a permanent adhesive. Useful adhesives include polyurethane resins, vinylic emulsions, such as those based on vinyl acetate or other vinyl esters, such as homopolymers and copolymers of ethylene and/or acrylic monomers (vinyl acrylics); homopolymers or copolymers of acrylic emulsions; a cross-linked adhesive including those created by including a reactive co-monomer (e.g., a monomer containing carboxyl, hydroxyl, epoxy, amide, isocyanate, etc. functionality) which are capable of cross-linking the polymer themselves (e.g. carboxyl groups reacting with hydroxyl, epoxy or isocyanate groups) or by reaction with an external cross-linker (e.g. urea-formaldehyde resin, isocyanates, polyols, epoxides, amines and metal salts, especially zinc). The adhesives herein can also include limited quantities of tackifying resins to improve adhesion, such as the addition of hydrogenated rosin ester tackifier to vinyl acetate/ethylene copolymer latex. See also the adhesive compositions in U.S. Pat. No. 5,969,025. Adhesives can be applied by, for example, spray coating to give a discontinuous attachment, curtain coating, roll coating, slot coating or lick coating to give a continuous attachment.

A suitable temporary attachment includes a weak adhesive, such as low peel force adhesive, repositionable adhesive, such as “PSA” (Pressure Sensitive Adhesive) having permanent tacks (some also called softgel or hydrogel adhesive, such as Dispomelt™ available from National Starch); a hook-and-loop fastening system (e.g. Velco™); a water-based, water-soluble coating or adhesive; an interlocking substrate shape that provides stability and an interlocking fit, and a combination thereof.

In one embodiment, the adhesive attachment is a liquid-impermeable adhesive material. Useful liquid-impermeable adhesive materiasl include PM17 and LA hotmelt from Savare (Milano, Italy), Propel™, SolarCure™, Optimelt™, Clarity™, Fullback™ hotmelts from Fuller (Minnesota, USA), Fulaprene, Bondseal solvent adhesive from Fuller, and Rakoll™, AirSperse™, LiquiLoc™, Casemate™, and water-based adhesives from Fuller.

Handle

The handle 50 may be comprised of any materials or materials as known in the art. In one embodiment, the handle 50 includes closed-cell foams of a polymer having a monomer selected from the group consisting of a urethane, a propylene, an ethylene, a butadiene, a styrene, vinyl acetate, a silicon, an ester, an acrylate, an ether, cellulose acetate, styrene, silicon, natural latex, rubber, vinylchloride, fluoroethylene, and mixtures thereof, available as Plastazote™, Evazote™, Supazote™, Propazote™ from Zotefoams plc (Croydon, UK) and FR, FM, CN or SD foam grade made with a significant fraction of hydrophobic polymer/materials.

Further, the handle 50 is temporarily attached to the film 30 in any manner as known in the art. Suitable temporary attachment include a weak adhesive, such as low peel force adhesive, repositionable adhesive, such as “PSA” (Pressure Sensitive Adhesive) having permanent tacks (some also called softgel or hydrogel adhesive, such as Dispomelt™ available from National Starch); a hook-and-loop fastening system (e.g. Velco™); a water-based, water-soluble coating or adhesive; an interlocking substrate shape that provides stability and an interlocking fit, and a combination thereof.

Active Agent

The cleaning implements herein may contain an active agent located anywhere as known in the art. In one embodiment, the active agent is impregnated in the erodible foam 20. In another embodiment, the active agent is placed between the erodible foam 20 and the film 30. IN yet another embodiment, the active agent is impregnated in the adhesive attachment 40. Suitable active agents are selected among a surfactant, a bleaching agent, a limescale reducing agent, a biocide, a solvent and a mixture thereof. In one embodiment, the active agent may have an HLB greater than about 5, alternatively greater than about 8 to about 14, alternatively greater than about 12. In another embodiment, the active agent may be present in free form in an amount from about 5% to about 20%, or from about 10% to about 15% by weight of the active agent. An active agent in free form means that the active agent is supplied to the cleaning implement in its neat form whose release from the cleaning implement is not purposefully controlled, delayed, or sustained.

Surfactants that are suitable for the present invention can be nonionic, anionic, cationic, amphoteric and/or a zwitterionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohol having the formula of RO(EO)e(PO)pH, where R is a hydrocarbon chain of from 2 to 24 carbon atoms, EO is ethylene oxide and PO is propylene oxide, e and p respectively representing the average degree of ethoxylation and propoxylation, are independently from 0 to 24, or R is a straight alkyl chain having from 6 to 22 carbon atoms, e is 5-12 and p is 0 (e.g. Lutensol™). Suitable cationic surfactants herein include derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds. Preferred cationic surfactants herein are trimethyl quaternary ammonium compounds. Suitable amphoteric surfactants herein include amine oxides, betaine or ammonium sulfate or ammonium carboxylate, having the following formula R₁R₂R₃NO, R₁R₂R₃NR₄SO₄ or R₁R₂R₃NR₄CO₂ wherein each of R₁, R₂ and R₃ is independently a saturated substituted or unsubstituted, linear or branched alkyl groups of from 1 to 30, or from 8 to 18 carbon atoms, except for R₄ which preferably contain 3 saturated carbons. Preferred amine oxides herein are for instance natural blend C₈-C₁₀ amine oxides, and C₁₂-C₁₆ amine oxides, such as cetyl dimethyl amine oxide. Preferred betaine herein is cocamidopropyl betaine and lauramidopropyl betaine. Suitable anionic surfactants include alkyl diphenyl ether sulphonate and alkyl carboxylate. Other suitable anionic surfactants herein include water soluble salts or acids of the formula ROSO₃M wherein R is preferably a C₁₀-C₂₄ hydrocarbyl, or C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation, such as sodium, potassium, lithium, or ammonium or substituted ammonium. Other suitable anionic surfactants include soap salts, C₉-C₂₀ linear alkylbenzenesulfonates, C₈-C₂₂ primary or secondary alkylsulfonates, sulfonated polycarboxylic acids, C₈-C₂₄ alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates, sulfates of alkylpolysaccharides, alkyl polyethoxy carboxylates, such as those of the formula RO(CH₂CH₂O)_(k)CH₂COO⁻M⁺ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable. Further examples are given in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678.

Bleaching agents herein may be selected from a hydrogen peroxide source, a preformed peroxycarboxylic acid, a hypohalite bleach source, and a mixture thereof. Hydrogen peroxide sources herein include persulfate, dipersulphate, persulfuric acid, percarbonate, perborate, metal peroxide, perphosphate, persilicate, urea peroxyhydrate and a mixture thereof. Preformed peroxycarboxylic acids herein include those containing one, two or more peroxy groups, and can be aliphatic or aromatic. When the organic percarboxylic acid is aliphatic, the unsubstituted acid suitably has the linear formula: HO—O—C(O)—(CH₂)_(n)—Y, wherein Y is H, CH₃, CH₂Cl, COOH or C(O)OOH; n is an integer of 1-20. Branched analogs are also acceptable. When the organic percarboxylic acid is aromatic, the unsubstituted acid suitably has formula: HO—O—C(O)—C₆H₄—Y wherein Y is hydrogen, alkyl, alkyhalogen, halogen, —COOH or 13 C(O)OOH.

Monoperoxycarboxylic acids useful as oxygen bleach herein are further illustrated by alkyl percarboxylic acids and aryl percarboxylic acids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-α-naphthoic acid; aliphatic, substituted aliphatic and arylalkyl monoperoxy acids such as peroxylauric acid, peroxystearic acid, and N,N-phthaloylaminoperoxycaproic acid (PAP); and 6-octylamino-6-oxo-peroxyhexanoic acid. Peracids can be used in acid form or any suitable salt with a bleach-stable cation. Suitable hypohalite bleaching agents herein include those that form positive halide ions and/or hypohalite ions, and bleaching agents that are organic based sources of halides, such as chloroisocyanurates. Suitable hypohalite bleaching agents herein include alkali metal and alkaline earth metal hypochlorite, hypobromite, hypoiodite, chlorinated trisodium phosphate dodecahydrate, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.

Limescale reducing agents herein include, but are not limited to, acids and chelating agents. Exemplary acids useful herein include hydrochloric acid, phosphoric acid, sulfuric acid, sulfamic acid, acetic acid, hydroxyacetic acid, citric acid, benzoic acid, tartaric acid, formic acid and mixtures thereof. A mixture of organic and inorganic acid is preferred. Chelating agents useful herein can include, but are not limited to, carboxylates, phosphates, phosphonates, polyfunctionally-substituted aromatic compounds, polyamines, biodegradable compounds, the alkali metal, ammonium or substituted ammonium salts or complexes of these chelating agents, and mixtures thereof. Further examples of suitable chelating agents and levels of use are described in U.S. Pat. Nos. 3,812,044; 4,704,233; 5,292,446; 5,445,747; 5,531,915; 5,545,352; 5,576,282; 5,641,739; 5,703,031; 5,705,464; 5,710,115; 5,710,115; 5,712,242; 5,721,205; 5,728,671; 5,747,440; 5,780,419; 5,879,409; 5,929,010; 5,929,018; 5,958,866; 5,965,514; 5,972,038; 6,172,021; and 6,503,876.

Biocide means any known ingredient having the ability of reducing or even eliminating by killing or removing the micro-organisms existing on a surface, such as those described in U.S. Pat. No. 6,613,728. Biocide useful herein includes a quaternary surface active compound, a guanidine, an alcohol, a glycerol, a phenolic compound, a heavy metal salt, an inorganic and organic acid, a halogen, a halogen-containing compound, a dye, an essential oil, an oxidizing compound, an adsorbent, a fungicide, an algaecide and a mixture thereof. Exemplary quaternary surface active compounds include benzalkonium chloride, benzethonium chloride, cetyl pyridinium chloride, sodium tetradecyl sulfate, sichlorobenzalkonium chloride, methylbenzethonium chloride, cetyl dimethyl ethyl ammonium bromide. Exemplary guanidines include chlorohexidine hydrochloride, chlorohexidine gluconate, dodecylguanidine hydrochloride, polyhexmethylenebiguanidine hydrochloride, and 6-acetoxy-2,4-dimethylmetadioxane. Exemplary alcohols include methanol, ethanol, propanol, isopropanol, etc. Exemplary phenolic compounds include cresol, resolcinols and related compounds, phenol; substituted phenols—cresols, meta-cresylacetate, creosote, quaiacol, resorcinol, hexylresorcinol, pyrogallol, thymol, thymol iodide, picric acid, chlorinated phenols--dichlorophene, hexachlorophene, tars. Exemplary halogens and halogen-containing compounds include iodine and iodoform. Exemplary oxidizing agents include peroxide, sodium perporate, potassium permanganate, zinc permanganate, potassium chlorate. Exemplary heavy metal salts include mercuric chloride, miscellaneous ionizable mercuric salts, organic mercurials, silver nitrate, silver lactate, silver picrate, silver proteins, silver halides, zinc oxide, zinc stearate, copper sulfate and organic tin derivatives. Exemplary dyes include azo dyes, acridene dyes, fluorescein dyes, phenolphthalein dyes and triphenylmethane dyes. Exemplary inorganic and organic acids include hydrochloric acid, sulfuric acid, nitric acid, citric acid, sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, and mixtures thereof. Exemplary essential oils are thyme oil, clove oil, cinnamon oil, geranium oil, eucalyptus oil, peppermint oil, citronella oil, ajowan oil, mint oil or mixtures thereof. Other useful biocide herein includes furan derivatives, nitrofurantoin, sulfur, sulfur dioxide, ichthamol, chrysarobin, anthralin, betanaphthol, balsams, volatile oils, chlorophyl.

Biocides useful herein also include fungicides and algaecides which act against molds and mildew. Removal of algae and fungi from hard surfaces is difficult. Moreover, fungi and algae reappear promptly if not completely removed or inhibited. Suitable fungicides and algaecides include metal salts, such as zinc sulfate, zinc acetate, zinc bromide, zinc chloride, zinc iodide, zinc nitrate, zinc bromate and zinc chlorate, cooper halide, copper sulfate, organic tin derivatives, water-insoluble or partially water-soluble fungicides and algaecides, such as diiodomethyl p-tolyl sulfone, N-(trichloromethyl thio) phthalimide, N,N-dimethyl-N′-phenyl N′-(fluorodichloromethyl thio) sulphamide, 2-(thiocyanomethylthio) benzothiazole/methylene bis(thiocyanate), 3-iodo-2-propynyl butyl carbamate, etc., all available from ALDRICH chemical. Above biocides are optionally mixed with concentrated acids, such as acetic acid, formic, propionic, n-butanoic, n-pentanoic, trimethylacetic, n-hexanoic, lactic, methoxyacetic, cyanoacetic, chloroacetic, citric, partaric, etc.

The active agent may be a solvent having a good dissolving ability for greasy stains. Solvents useful herein include those which are at least partially water-miscible, such as alcohols, ethers, such as diethylene glycol diethylether, diethylene glycol dimethylether, propylene glycol dimethylether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycol monopropylether, propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene glycol monomethylether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, diethyleneglycol monobutylether, lower esters of monoalkylethers of ethylene glycol or propylene glycol, such as propylene glycol monomethyl ether acetate, N-methyl pyrolidone and tetrahydrofuran. Mixtures of several solvents can also be used.

Packaging Means

The cleaning implement herein may be combined in an article of manufacture with a packaging means known for packaging cleaning implements. Particularly suitable packaging means herein can be paper bags, plastic bags, plastic bins, cartons, carton boxes, flow wraps, plastic wraps, and paper wraps, and the like and combinations thereof. Multiple uses of the cleaning implement and/or components thereof may be packed together.

Method of Cleaning a Hard Surface

The present invention encompasses a method of cleaning a surface by rubbing a cleaning implement herein against a hard surface. “Cleaning” means removing spots and/or stains from surfaces. Suitable surfaces include tiles, walls, floors, sanitary fittings such as sinks, showers, shower curtains, wash basins, toilets, household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, and dishwashers. The method of cleaning a surface may additionally include the step of wetting the cleaning implement with an appropriate solvent, such as tap water, prior to bringing the cleaning implement into contact with said hard surface

It should be understood that the present invention includes various modifications that can be made to the embodiments of the cleaning article as described herein as come within the scope of the appended claims and their equivalents.

In all embodiments of the invention, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise. All ranges are inclusive and combinable. The number of significant digits conveys neither a limitation on the indicated amounts nor on the accuracy of the measurements. All numerical amounts are understood to be modified by the word “about” unless otherwise specifically indicated. All such weights as they pertain to listed ingredients are based on the active level and do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.

It should be understood that every maximum numerical limitation given throughout this specification would include every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

Every document cited herein, including any cross referenced or related patent or application is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern. 

What is claimed is:
 1. A cleaning implement comprising: a) an erodible foam adapted to contact a surface to be cleaned, and b) a hydrophobic film attached to the erodible foam, wherein the erodible foam is adhered to the hydrophobic film with an adhesive attachment.
 2. The cleaning implement of claim 1, wherein the erodible foam is heat-compressed.
 3. The cleaning implement of claim 2, wherein the heat-compressed erodible foam has an average pore size of about 50 μm to about 250 μm.
 4. The cleaning implement of claim 2, wherein the heat-compressed erodible foam has an average pore size of about 80 microns to about 150 microns.
 5. The cleaning implement of claim 2, wherein the heat-compressed erodible foam substrate has a density of about 18 kg/m³ to about 25 kg/m³.
 6. The cleaning implement of claim 2, wherein the heat-compressed erodible foam substrate is a heat-compressed melamine foam substrate.
 7. The cleaning implement of claim 1, wherein the erodible foam has a thickness of at least about 5 mm.
 8. The cleaning implement of claim 1, further comprising a handle attached to the hydrophobic film.
 9. The cleaning implement of claim 1, further comprising an active agent impregnated in the erodible foam.
 10. The cleaning implement of claim 9, wherein the active agent is selected from the group consisting of surfactants, bleaching agents, limescale reducing agents, biocides, solvents, and mixtures thereof.
 11. A cleaning implement comprising: a) an erodible foam adapted to contact a surface to be cleaned, and b) a impermeable film attached to the erodible foam, wherein erodible foam is adhered to the film with an adhesive attachment.
 12. The cleaning implement of claim 11, wherein the erodible foam is heat-compressed.
 13. The cleaning implement of claim 12, wherein the heat-compressed erodible foam has an average pore size of about 50 μm to about 250 μm.
 14. The cleaning implement of claim 12, wherein the heat-compressed erodible foam has an average pore size of about 80 microns to about 150 microns.
 15. The cleaning implement of claim 12, wherein the heat-compressed erodible foam substrate has a density of about 18 kg/m³ to about 25 kg/m³.
 16. The cleaning implement of claim 12, wherein the heat-compressed erodible foam substrate is a heat-compressed melamine foam substrate.
 17. The cleaning implement of claim 11, wherein the erodible foam has a thickness of at least about 5 mm.
 18. The cleaning implement of claim 11, further comprising a handle attached to the hydrophobic film.
 19. The cleaning implement of claim 11, further comprising an active agent impregnated in the erodible foam.
 20. The cleaning implement of claim 19, wherein the active agent is selected from the group consisting of surfactants, bleaching agents, limescale reducing agents, biocides, solvents, and mixtures thereof.
 21. A method of cleaning a surface comprising the steps of: a) providing a cleaning implement comprising an erodible foam substrate, an impermeable film attached adhered to the film with an adhesive attachment, and a handle attached to the impermeable film; and b) rubbing said cleaning implement against a surface.
 22. The method of claim 21 further comprising the step of wetting the cleaning implement with an appropriate solvent prior to step b. 